Sizing composition for mineral wool comprising a monosaccharide and/or a polysaccharide and an organic polycarboxylic acid, and insulating products obtained

ABSTRACT

A sizing composition for insulating products based on mineral wool, in particular on glass or on rock, includes at least one monosaccharide and/or at lest one polysaccharide, and at least one organic polycarboxylic acid having a molar mass of less than or equal to 1000. Another subject-matter of the present invention is the insulating products based on mineral fibres thus obtained and the process for the manufacture thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the U.S. National Stage of PCT/FR2008/052203, filedDec. 4, 2008, which in turn claims priority to French Application No.0759580, filed Dec. 5, 2007. The content of both applications areincorporated herein by reference in their entirety.

The present invention relates to the field of thermal and/or acousticinsulating products based on mineral wool, in particular glass or rock,and on a formaldehyde-free organic binder.

The invention more particularly relates to a sizing composition capableof crosslinking to form the said organic binder, which includes at leastone monosaccharide and/or one polysaccharide and at least one organicpolycarboxylic acid having a molar mass of less than 1000, to theprocess for the preparation of the said sizing composition and to theinsulating products which result therefrom.

The manufacture of insulating products based on mineral wool generallycomprises a stage of manufacture of the wool itself, which can becarried out by various processes, for example according to the knowntechnique of fiberizing by internal or external centrifugation. Thecentrifugation consists in introducing the molten mineral material(glass or rock) into a centrifugal device comprising a multitude ofsmall orifices, the material being projected towards the peripheral wallof the device under the action of the centrifugal force and escapingtherefrom in the form of filaments. On leaving the centrifugal device,the filaments are drawn and carried towards a receiving member by a gasstream having a high temperature and a high speed, in order to form aweb of fibres (or mineral wool) there.

In order to provide for the assembly of the fibres together and to makeit possible for the web to have cohesion, a sizing compositioncomprising a thermosetting resin is projected onto the fibres, on theroute between the outlet of the centrifugal device and the receivingmember. The web of fibres coated with the size is subjected to a heattreatment, at a temperature generally of greater than 100° C., in orderto bring abut the polycondensation of the resin and to thus obtain athermal and/or acoustic insulating product having specific properties,in particular dimensional stability, tensile strength, thicknessrecovery after compression and homogeneous colour.

The sizing composition to be projected onto the mineral wool isgenerally provided in the form of an aqueous solution including thethermosetting resin and additives, such as a catalyst for thecrosslinking of the resin, an adhesion-promoting silane, adust-preventing mineral oil, and the like. The sizing composition isgenerally applied to the fibres by spraying.

The properties of the sizing composition depend largely on thecharacteristics of the resin. From the viewpoint of the application, itis necessary for the sizing composition to exhibit good sprayability andto be able to be deposited at the surface of the fibres in order toefficiently bind them.

The resin has to be stable for a given period of time before being usedto form the sizing composition, which composition is generally preparedat the time of use by mixing the resin and the additives mentionedabove.

At the regulatory level, it is necessary for the resin to be regarded asnon-polluting, that is to say for it to comprise—and for it generateduring the sizing stage or subsequently—as little as possible in the wayof compounds which may be harmful to human health or to the environment.

The thermosetting resins most commonly used are phenolic resinsbelonging to the family of the resols. In addition to their goodcrosslinkability under the abovementioned thermal conditions, theseresins are soluble in water, have a good affinity for mineral fibres, inparticular glass fibres, and are relatively inexpensive.

These resols are obtained by condensation of phenol and formaldehyde, inthe presence of a basic catalyst, in a formaldehyde/phenol molar ratioof greater than 1, so as to promote the reaction between the phenol andthe formaldehyde and to reduce the level of residual phenol in theresin. The condensation reaction between the phenol and the formaldehydeis carried out while limiting the degree of condensation of themonomers, in order to avoid the formation of long, relativelywater-insoluble, chains which reduce the dilutability. Consequently, theresin comprises a certain proportion of unreacted monomer, in particularformaldehyde, the presence of which is undesirable because of its knownharmful effects.

For this reason, resol-based resins are generally treated with urea,which reacts with the free formaldehyde by trapping it in the form ofnonvolatile urea-formaldehyde condensates. The presence of urea in theresin in addition brings a certain economic advantage as a result of itslow cost because it is possible to introduce it in a relatively largeamount without affecting the operating qualities of the resin, inparticular without harming the mechanical properties of the finalproduct, which significantly lowers the total cost of the resin.

Nevertheless, it has been observed that, under the temperatureconditions to which the web is subjected in order to obtain crosslinkingof the resin, the urea-formaldehyde condensates are not stable; theydecompose with restoration of the formaldehyde and urea, in its turn atleast partially decomposed to give ammonia, which are released into theatmosphere of the factory.

Regulations with regard to environmental protection, which are becomingmore restrictive, are forcing manufacturers of insulating products tolook for solutions which make it possible to further lower the levels ofundesirable emissions, in particular of formaldehyde.

Solutions in which resols are replaced in sizing compositions are knownand are based on the use of a carboxylic acid polymer, in particular anacrylic acid polymer.

In U.S. Pat. No. 5,340,868, the size comprises a polycarboxylic polymer,a β-hydroxyamide and an at least trifunctional monomeric carboxylicacid.

Provision has been made for sizing compositions comprising apolycarboxylic polymer, a polyol and a catalyst, which catalyst is aphosphorus-comprising catalyst (U.S. Pat. No. 5,318,990, U.S. Pat. No.5,661,213, U.S. Pat. No.6,331,350, U.S. 2003/0008978), a fluoroborate(U.S. Pat. No. 5,977,232) or else a cyanamide, a dicyanamide or acyanoguanidine (U.S. Pat. No. 5,932,689).

A description has also been given of sizing compositions comprising analkanolamine including at least two hydroxyl groups and a polycarboxylicpolymer (U.S. Pat. No. 6,071,994, U.S. Pat. No. 6,099,773, U.S. Pat. No.6,146,746) in combination with a copolymer (U.S. Pat. No. 6,299,936).

In U.S. 2002/0091185, the polycarboxylic polymer and the polyol are usedin amounts such that the ratio of the number of equivalents of OH groupsto the number of equivalents of COOH groups varies from 0.6/1 to 0.8/1.

In U.S. 2002/0188055, the sizing composition comprises a polycarboxylicpolymer, a polyol and a cationic, amphoteric or nonionic surfactant.

In U.S. 2004/0002567, the sizing composition includes a polycarboxylicpolymer, a polyol and a coupling agent of silane type.

In U.S. 2005/0215153, a description is given of a size formed by aprebinder comprising polymer of carboxylic acid and of a polyol, andfrom a dextrin as cobinder.

Furthermore, an adhesive composition based on heat-crosslinkablepolysaccharides which can be used as size for mineral wool is known(U.S. Pat. No. 5,895,804). The composition comprises a polycarboxylicpolymer having at least two carboxylic acid functional groups and amolecular weight at least equal to 1000 and a polysaccharide having amolecular weight at least equal to 10 000.

The aim of the present invention is to provide a sizing composition forinsulating products based on mineral wool which is devoid offormaldehyde, thus making it possible to have available an alternativeto the sizing compositions based on resols.

Another aim is to provide a sizing composition prepared from naturalcompounds resulting from renewable sources, in particular plant sources,or produced by microbial fermentation.

In order to achieve these aims, the present invention provides a sizingcomposition for insulating products based on mineral wool, in particularon glass or rock, which comprises:

at least one monosaccharide and/or at least one polysaccharide, and

at least one organic polycarboxylic acid having a molar mass of lessthan or equal to 1000.

The monosaccharide is chosen from monosaccharides including from 3 to 8carbon atoms, preferably aldoses and advantageously aldoses comprisingfrom 5 to 7 carbon atoms. The aldoses which are particularly preferredare natural aldoses (belonging to the D series), in particular hexoses,such as glucose, mannose and galactose.

The polysaccharide in accordance with the invention is chosen frompolysaccharides having a weight-average molar mass of less than 100 000,preferably of less than 50 000, advantageously of less than 10 000 andbetter still of greater than 180.

Advantageously, the polysaccharide exhibits a polydispersity index (PI),defined by the ratio of the weight-average molar mass to thenumber-average molar mass, which is less than or equal to 10.

Preferably, the polysaccharide includes at least one unit chosen fromthe abovementioned aldoses, advantageously glucose. The polysaccharideswhich are predominantly (to more than 50% by weight) composed of glucoseunits are particularly preferred.

According to a preferred embodiment, the invention uses a mixture ofmonosaccharide(s) and/or of polysaccharide(s), obtained in particularfrom plants, especially a dextrin or a molasses.

Dextrins are compounds corresponding to the general formula(C₆H₁₀O₅)_(n) obtained by partial hydrolysis of starch. The processesfor the preparation of dextrins are known. For example, dextrins can beprepared by heating or by drying to dryness a starch, generally in thepresence of an acid catalyst, which results in the constituent amyloseand amylopectin molecules of the said starch being ruptured to giveproducts of lower molar mass. Dextrins can also be obtained by treatingthe starch enzymatically with one or more amylases, in particularmicrobial amylases, capable of hydrolyzing the bonds of the starch. Thenature of the treatment (chemical or enzymatic) and the hydrolysisconditions have a direct effect on the average molar mass and thedistribution of the molar masses of the dextrin.

The dextrins in accordance with the invention can be obtained fromstarch or starch derivatives of varied plant origin, for exampleresulting from tubers, such as potato, manioc, maranta and sweet potato,resulting from grains, such as wheat, corn, rye, rice, barley, millet,oats and sorghum, resulting from fruit, such as horse chestnut, sweetchestnut and hazelnut, or resulting from leguminous plants, such as peasand beans.

Preference is given in particular to dextrins having a dextroseequivalent DE of greater than or equal to 5, preferably of greater thanor equal to 10, advantageously of greater than or equal to 15 and betterstill of less than 100.

Conventionally, the dextrose equivalent DE is defined by the followingrelationship:

${DE} = {100 \times \left( \frac{{number}\mspace{14mu}{of}\mspace{14mu}{glycoside}\mspace{11mu}{bonds}\mspace{14mu}{cleaved}}{{number}\mspace{14mu}{of}{\mspace{11mu}\;}{glycoside}\mspace{14mu}{bonds}\mspace{11mu}{in}\mspace{14mu}{the}\mspace{14mu}{starting}\mspace{14mu}{starch}} \right)}$

The molasses are residues from the refining of sugar extracted inparticular from cane and beet which comprise a high content of glucides,of the order of 40 to 60% by weight. Sucrose constituents the bulk ofthe glucides of the molasses.

The molasses in accordance with the invention preferably include from 45to 50% by weight of total glucides, expressed as sucrose.

Beet molasses are particularly preferred. The term “organicpolycarboxylic acid” is understood to mean an organic acid comprising atleast two carboxyl functional groups, preferably at most 4 carboxylfunctional groups and advantageously at most 3 carboxyl functionalgroups.

The organic polycarboxylic acid acts as crosslinking agent; it iscapable of reacting with the monosaccharide(s) and/or polysaccharide(s)under the effect of heat to form ester bonds which result in a polymericnetwork being obtained in the final binder. The said polymeric networkmakes it possible to establish bonds at the junction points of thefibres in the mineral wool.

The organic polycarboxylic acid is chosen from organic polycarboxylicacids exhibiting a molar mass of less than or equal to 1000, preferablyof less than or equal to 750 and advantageously of less than or equal to500.

Preferably, the organic polycarboxylic acid is a saturated orunsaturated and linear or branched alicyclic acid, a cyclic acid or anaromatic acid.

The organic polycarboxylic acid can be a dicarboxylic acid, for exampleoxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid,tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaricacid, itaconic acid, maleic acid, traumatic acid, camphoric acid,phthalic acid and its derivatives, in particular comprising at least oneboron or chlorine atom, tetrahydrophthalic acid and its derivatives, inparticular comprising at least one chlorine atom, such as chlorendicacid, isophthalic acid, terephthalic acid, mesaconic acid and citraconicacid, or a dicarboxylic acid precursor, in particular an anhydride, suchas maleic anhydride, succinic anhydride and phthalic anhydride; atricarboxylic acid, for example citric acid, tricarballylic acid,1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid,trimellitic acid and trimesic acid; or a tetracarboxylic acid, forexample 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid.

In the sizing composition, the monosaccharide and/or the polysacchariderepresents from 10 to 90% of the weight of the mixture composed of themonosaccharide and/or the polysaccharide and the organic polycarboxylicacid, preferably from 20 to 85% and advantageously from 30 to 80%.

The sizing composition can additionally comprise an acid or basiccatalyst which has in particular the role of adjusting the temperatureat which crosslinking begins.

The catalyst can be chosen from Lewis bases and acids, such as clays,colloidal or noncolloidal silica, organic amines, quaternary amines,metal oxides, metal sulphates, metal chlorides, urea sulphates, ureachlorides and catalysts based on silicates.

The catalyst can also be a phosphorus-comprising compound, for examplean alkali metal hypophosphite salt, an alkali metal phosphite, an alkalimetal polyphosphate, an alkali metal hydrogenphosphate, a phosphoricacid or an alkylphosphonic acid. Preferably, the alkali metal is sodiumor potassium.

The catalyst can also be a compound comprising fluorine and boron, forexample tetrafluoroboric acid or a salt of this acid, in particular analkali metal tetrafluoroborate, such as sodium tetrafluoroborate orpotassium tetrafluoroborate, an alkaline earth metal tetrafluoroborate,such as calcium tetrafluoroborate or magnesium tetrafluoroborate, a zinctetrafluoroborate and an ammonium tetrafluoroborate.

Preferably, the catalyst is sodium hypophosphite, sodium phosphite andthe mixtures of these compounds.

The amount of catalyst introduced into the sizing composition canrepresent up to 20% of the weight of the monosaccharide and/orpolysaccharide and organic polycarboxylic acid, preferably up to 10%,and advantageously is at least equal to 1%.

The sizing composition in accordance with the invention can additionallycomprise the conventional additives below in the following proportions,calculated on the basis of 100 parts by weight of monosaccharide(s)and/or polysaccharide(s) and organic polycarboxylic acid:

-   -   from 0 to 2 parts of silane, in particular an aminosilane,    -   from 0 to 20 parts of oil, preferably from 4 to 15 parts,    -   from 0 to 30 parts of urea and/or of glycerol, preferably from 0        to 20 parts,    -   from 0 to 5 parts of a silicone,    -   from 0 to 30 parts of an “extender” chosen from lignin        derivatives, such as ammonium lignosulphonate (ALS) or sodium        lignosulphonate, and animal or plant proteins.

The role of the additives is known and is briefly restated: the silaneis an agent for coupling between the fibres and the binder, and alsoacts as anti-ageing agent; the oils are dust-preventing and hydrophobicagents; the urea and the glycerol act as plasticizers and make itpossible to prevent pregelling of the sizing composition; the siliconeis a hydrophobic agent, the function of which is to reduce theabsorption of water by the insulating product; the “extender” is anorganic filler, soluble or dispersible in the aqueous sizingcomposition, which makes it possible in particular to reduce the cost ofthe sizing composition.

The sizing composition exhibits an acidic pH, of the order of 1 to 5according to the organic polycarboxylic acid used, preferably of greaterthan or equal to 1.5. Advantageously, the pH is maintained at a value atleast equal to 2, so as to limit problems of instability of the sizingcomposition and of corrosion of the manufacturing line, by virtue of theaddition of an amino compound which is incapable of reacting with themonosaccharide and/or the polysaccharide, for example a tertiary amine,in particular triethanolamine. The amount of amino compound canrepresent up to 30 parts by weight of the total weight of monosaccharideand/or of polysaccharide and of organic polycarboxylic acid.

The sizing composition is intended to be applied to mineral fibres, inparticular glass or rock fibres.

Conventionally, the sizing composition is projected onto the mineralfibres at the outlet of the centrifugal device and before they arecollected on the receiving member in the form of a web of fibres whichis subsequently treated at a temperature which makes possible thecrosslinking of the size and the formation of an infusible binder. Thecrosslinking of the size according to the invention takes place at atemperature comparable to that of a conventional formaldehyde-phenolresin, at a temperature of greater than or equal to 110 ° C., preferablyof greater than or equal to 130° C. and advantageously of greater thanor equal to 140° C.

The acoustic and/or thermal insulating products obtained from thesesized fibres also constitute a subject-matter of the present invention.

These products are generally provided in the form of a mat or felt ofmineral wool, of glass or of rock, or also of a veil of mineral fibres,also of glass or of rock, intended in particular to form a surfacecoating on the said mat or felt.

The following examples make it possible to illustrate the inventionwithout, however, limiting it.

In these example, the following are measured:

the weight-average molar mass and the number-average molar mass of thedextrins by gel permeation chromatography under the followingconditions:

-   -   three columns arranged in series: two ViscoGEL® columns filled        with GMPWxI (“mixed bed” columns) and one ViscoGEL® column        filled with G2500PWxI (“single bed” column). These columns are        sold by Viscotek    -   eluent: PBS buffer (saline solution based on sodium chloride and        phosphate with a pH of approximately 7.4)    -   temperature: 35° C.    -   detectors: differential refractometry, viscosimetry and light        scattering,

the crosslinking start temperature (T_(C)) and the crosslinking rate (R)by the Dynamic Mechanical Analysis (DMA) method, which makes it possibleto characterize the viscoelastic behaviour of a polymeric material. Theprocedure is as follows: a sample of Whatman paper is impregnated withthe sizing composition (content of organic solids of the order of 40%)and is then fixed horizontally between two jaws. An oscillatingcomponent equipped with a device for measuring the stress as a functionof the strain applied is positioned on the upper face of the sample. Thedevice makes it possible to calculate the modulus of elasticity E. Thesample is heated to a temperature varying from 20 to 250° C. at a rateof 4° C/min. The curve of variation in the modulus of elasticity E (inMPa) as a function of the temperature (in ° C.) is plotted from themeasurements, the general appearance of the curve being given in FIG. 1.FIG. 1 shows the variation in the modulus of elasticity E (in MPa) as afunction of the temperature (in ° C.) from measurements according to anembodiment. The values corresponding to the crosslinking starttemperature (T_(C)), in ° C., and the slope corresponding to thecrosslinking rate (R), in MPa/° C., are determined on the curve.

the contact angle of the sizing composition on a glass substrate.

the tensile strength according to Standard ASTM C 686-71T on a samplecut out by stamping from the insulating product. The sample has theshape of a torus with a length of 122 mm, a width of 46 mm, a radius ofcurvature of the cut-out of the outer edge equal to 38 mm and a radiusof curvature of the cut-out of the inner edge equal to 12.5 mm.

The sample is positioned between two cylindrical mandrels of a testmachine, one of which is moveable and is moved at a constant rate. Thebreaking force F (in gram-force) of the sample is measured and thetensile strength TS, defined by the ratio of the breaking force F to theweight of the sample, is calculated.

The tensile strength is measured after manufacture (initial tensilestrength) and after accelerated ageing in an autoclave at a temperatureof 105° C. under 100% relative humidity for 15 minutes (TS 15).

the initial thickness of the insulation product and the thickness aftercompressing for 1 hour, 24 hours, 30 days and 90 days with a degree ofcompression (defined as being the ratio of the nominal thickness to thethickness under compression) equal to 6/1 (Examples 22 to 24) or 5/1(Examples 25 to 34). The thickness measurements make it possible toevaluate the good dimensional behaviour of the product.

the water absorption under the conditions of Standard EN 1609, expressedas kg of water absorbed per m² of insulating product. The insulatingproducts exhibiting a water absorption of less than 1 kg/m² are regardedas having a low short-term (24 hours) water absorption; they belong tothe “WS” category according to the ACERMI certification.

the five resistance measured according to Standard EN ISO 1182. Theproducts belonging to the “Euroclass A1” class do not contribute to thedeclaration and to the propagation of the fire.

the thermal conductivity coefficient λ according to Standard EN 13162,expressed in W/(m×°K).

the amount of formaldehyde emitted by the product after testing for 3days under the conditions of Standard ISO 16000-9 and with a ratio ofthe change in air to the level of charging of the chamber Q equal to0.4. The amount of formaldehyde is measured according to the methoddescribed in Standard ISO 16000-3. The results are expressed in μg offormaldehyde emitted per m² and per hour.

EXAMPLES 1 TO 6

Sizing compositions are prepared which comprise the constituentsappearing in Table 1, expressed as parts by weight.

The molasses is a beet molasses for industrial use (sold by FranceMélasses) which is provided in the form of a viscous and homogeneousliquid comprising from 43 to 53% by weight of sugars, expressed assucrose.

The sizing compositions are prepared by successively introducing, into avessel containing water, the molasses, citric acid and sodiumhypophosphite (catalyst) with vigorous stirring until the constituentshave completely dissolved.

The properties of the sizing compositions which appear in Table 1 areevaluated in comparison with a conventional sizing composition includinga formaldehyde-phenol resin and urea (Reference) prepared in accordancewith Example 2, Test 1, of WO 01/96254 A1.

The sizing compositions of Examples 1 to 6 have similar properties tothose of the Reference in terms of crosslinking start temperature(T_(c)), of viscosity and of contact angle. The crosslinking rate (R)remains lower than that of the Reference.

EXAMPLES 7 TO 21

The operation is carried out under the conditions of Example 1 to 6modified in that use is made of a dextrin resulting from corn starch(maltodextrin) having the following characteristics:

a weight-average molar mass equal to 5500, a polydispersity index PIequal to 9.5 and a dextrose equivalent DE of between 16.5 and 19.5 (soldunder the reference 419699 by Aldrich; solids contents: 100%): Examples7 to 12,

a weight-average molar mass equal to 1850, a polydispersity index PIequal to 4.45 and a dextrose equivalent DE equal to 30 (sold under thereference Tackidex® 30L75 by Roquette Frères; solids content: 75%):Examples 13 to 15,

a weight-average molar mass equal to 1520, a polydispersity index PIequal to 5.72 and a dextrose equivalent DE equal to 62 (sold under thereference Flolys® B6080S by Roquette Frères; solids content: 81%):Examples 16 to 18,

a glucose content by weight of greater than 95% and a dextroseequivalent DE equal to 99 (sold under the reference glucose syrup74/968® by Roquette Frères; solids content: 75%): Examples 19 to 21.

The contents of the constituents of the sizing compositions are given inTable 2, in parts by weight.

The sizing compositions of Examples 8 to 15, 18 and 21 advantageouslyexhibit a lower crosslinking start temperature (T_(c)) than that of theReference, The presence of the catalyst in the composition of Example 9makes it possible to significantly reduce the crosslinking starttemperature in comparison with the composition of Example 7, with,however, a reduction in the crosslinking rate (R).

The sizing compositions according to the invention exhibit a lowviscosity, similar to that of the Reference, for the same solids content(40%), indeed even lower, which allows good application to the mineralfibres, in particular when application is carried out by spraying.

These compositions also exhibit a similar contact angle to that of theReference, which denotes good wettability of the fibres by the sizingcomposition.

EXAMPLES 22 TO 24

The compositions of Examples 2, 4 and 10, and also theformaldehyde-phenol resin (Reference), are used to form insulationproducts based on glass wool.

Glass wool is manufactured by the internal centrifugation technique inwhich the molten glass composition is converted into fibres by means ofa tool, referred to as centrifuging disc, comprising a basket forming achamber for receiving the molten composition and a peripheral bandpierced by a multitude of orifices: the dish is rotated about itsvertically positioned axis of symmetry, the composition is ejectedthrough the orifices under the effect of the centrifugal force and thematerial escaping from the orifices is drawn into fibres with theassistance of a drawing gas stream.

Conventionally, a size spraying ring is positioned beneath thefiberizing disc so as to uniformly distribute the sizing compositionover the glass wool which has just been formed.

The mineral wool, thus sized, is collected on a belt conveyor equippedwith internal extraction boxes which hold the mineral wool in the formof a felt or web at the surface of the conveyor. The felt or the web iscut up and then placed in an oven maintained at 220° C. where theconstituents of the size polymerize to form a binder.

The values of the tensile strength before and after ageing, and theinitial thickness and the recovery in thickness after compressing for 24hours and 30 days, are collated in Table 3.

EXAMPLES 25 TO 34

These examples illustrate the manufacture of insulating products on anindustrial line.

The mineral wool is continuously produced under the conditions ofExamples 22 to 24 on a line with a width of 2.40 m. The mineral woolcoated with the sizing composition subsequently passes continuously intoan oven at 290° C.

The insulating product obtained at the outlet of the oven exhibits athickness of the order of 82 mm, a density equal to 17.5 kg/m³ and aloss on ignition equal to 5%.

The sizing compositions used are prepared by introducing theconstituents of Table 4 with stirring into a vessel containing water.

The properties of the insulating products are evaluated in comparisonwith the reference sizing composition (recorded as Ref.) described inExamples 1 to 6. The measurements appear in Table 4.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ref. Composition Molasses 3040 50 60 70 80 — Citric acid 70 60 50 40 30 20 — Sodium hypophosphite 55 5 5 5 5 — Properties Crosslinking start 151 149 149 155 156 156 151temperature T_(c) (° C.) Crosslinking rate R 58 69 65 59 40 41 161(MPa/° C.) Viscosity at 25° C. 7.8 7.8 8.0 7.8 7.2 7.5 8.0 (mPa · s) ⁽¹⁾Viscosity at 50° C. 5.9 6.0 5.9 6.1 5.8 6.0 6.0 (mPa · s) ⁽¹⁾ Contactangle (°) ⁽¹⁾ 4 6 8 12 11 12 10 ⁽¹⁾ solution with a solids content of40%

TABLE 2 Example 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Ref.Composition Dextrin 419699 40 30 40 50 60 70 — — — — — — — — — —Tackidex 30L75 — — — — — — 80 70 60 — — — — — — — Flolys — — — — — — — —— 80 70 60 — — — — Glucose syrup 74/968 — — — — — — — — — — — — 80 70 60— Citric acid 60 70 60 50 40 30 20 30 40 20 30 40 20 30 40 — Sodiumhypophosphite 0 5 5 5 5 5 5 5 5 5 5 5 5 5 5 — Properties Crosslinkingstart temperature 171 144 132 131 132 130 120 120 120 152 151 120 165151 135 151 T_(c) (° C.) Crosslinking rate R (MPa/° C.) 105 62 63 67 7276 27 45 57 42 48 46 67 42 32 161 Viscosity at 25° C. (mPa · s) ⁽¹⁾ 9.39.4 10.0 11.0 12.0 12.0 7.4 7.0 7.0 6.6 6.4 6.0 6.2 5.9 5.5 8.0Viscosity at 50° C. (mPa · s) ⁽¹⁾ 6.8 7.1 7.6 7.9 9.3 8.6 5.3 5.0 5.15.2 5.4 5.0 5.0 4.7 4.6 6.0 Contact angle (°) ⁽¹⁾ 6.0 6.0 6.0 8.0 8.012.0 5.7 5.9 6.0 11.9 11.0 10.8 9.5 9.0 8.1 10.0 ⁽¹⁾ solution with asolids content of 40%

TABLE 3 Ex. 22 Ex. 23 Ex. 24 Ref. Sizing composition Ex. 2 Ex. 4 Ex. 10Ref. Tensile strength Before ageing 298 260 226 336 After ageing 220 175180 280 Loss (%) 26.2 32.7 20.3 16.7 Thickness (mm) Initial 134 134 143127 24 hours 89 90 94 102 30 days 81 80 91 98

TABLE 4 Example 25 26 27 28 29 30 Sizing composition Glucose syrup74/968 49.0 49.0 49.0 64.0 34.3 34.3 Tackidex 30L75 — — — — — — RoclysC3072S⁽²⁾ — — — — — — Citric acid 51.0 51.0 51.0 36.0 47.2 47.2 Sodiumhypophosphite 5.0 2.8 2.8 5.0 5.0 5.0 Glycerol — — 10 — — —γ-Aminopropyltriethoxysilane 1.0 1.0 1.0 1.0 1.0 1.0 Mineral oil 9.5 9.59.5 — 9.5 9.5 Silicone — — — — — 1.0 Triethanolamine — — — — 18.5 18.5pH n.d. n.d. n.d. 1.60 2.80 2.80 Insulation product Tensile strength(gf/g) Before ageing 318 308 356 404 431 389 After ageing 278 314 325323 332 274 Loss (%) 13 −2 9 20 23 30 Thickness (mm) 1 hour 81.1 78.877.0 80.8 79.8 79.6 24 hours 78.4 75.2 71.1 76.2 78.1 78.3 30 days 78.474.1 71.1 75.0 76.9 77.4 90 days 73.6 74.4 72.4 n.d. n.d. n.d. Waterabsorption (kg/m³) n.d. 0.44 0.77 2.56 1.65 0.62 Fire resistance(Euroclass A1) n.d. yes n.d. n.d. n.d. n.d. λ (W/(m × ° K) 0.0336 0.03360.0336 0.0332 n.d. 0.0344 Formaldehyde emitted (μg/m²/h) n.d. <0.8 n.d.n.d. <0.8 n.d. Example 31 32 33 34 Ref. Sizing composition Glucose syrup74/968 — — — — — Tackidex 30L75 55.0 55.0 — — — Roclys C3072S⁽²⁾ — —62.0 39.2 — Citric acid 45.0 45.0 38.0 43.6 — Sodium hypophosphite 2.82.8 5.0 5.0 — Glycerol — 10.0 — 5.0 — γ-Aminopropyltriethoxysilane 1.01.0 1.0 1.0 — Mineral oil 9.5 9.5 9.5 9.5 — Silicone — — — — —Triethanolamine — — — 17.0 — pH n.d. n.d. 1.49 2.75 4.92 Insulationproduct Tensile strength (gf/g) Before ageing 304 355 382 385 459 Afterageing 294 310 337 324 389 Loss (%) 3 13 12 16 15 Thickness (mm) 1 hour83.8 81.1 80.8 81.6 78.3 24 hours 77.2 75.0 78.4 78.0 74.0 30 days 75.273.1 68.8 77.3 72.2 90 days 78.7 75.3 n.d. n.d. 73.8 Water absorption(kg/m³) 7.31 7.01 n.d. n.d. 0.97 Fire resistance (Euroclass A1) yes n.d.n.d. n.d. yes λ (W/(m × ° K) 0.0336 0.0337 0.0347 0.0345 0.0332Formaldehyde emitted (μg/m²/h) <0.8 n.d. n.d. n.d. 22-25 n.d.: notdetermined ⁽²⁾dextrin resulting from corn starch; weight-average molarmass: 3510; polydispersity index PI: 5.2; dextrose equivalent DE: 30;sold by Roquette Frères

What is claimed is:
 1. A sizing composition for insulating productsbased on mineral wool, the composition comprising: at least onemonosaccharide and/or at least one polysaccharide having aweight-average molar mass of less than 10000, and at least onenon-polymeric organic polycarboxylic acid having a molar mass of lessthan 1000, wherein the at least one non-polymeric organic polycarboxylicacid represents at least 10% of a weight of the mixture composed of theat least one monosaccharide and/or the at least one polysaccharide andthe at least one non-polymeric organic polycarboxylic acid.
 2. Thecomposition of claim 1, wherein the at least one monosaccharide ischosen from monosaccharides including from 3 to 8 carbon atoms.
 3. Thecomposition of claim 2, wherein the at least one monosaccharide ischosen from monosaccharides including from 5 to 7 carbon atoms.
 4. Thecomposition of claim 2, wherein the at least one monosaccharide is analdose.
 5. The composition of claim 4, wherein the aldose is a hexose.6. The composition of claim 5, wherein the hexose is glucose, mannose orgalactose.
 7. The composition of claim 1, wherein the at least onepolysaccharide is composed to more than 50% of glucose units.
 8. Thecomposition of claim 1, comprising a mixture of the at least onemonosaccharide and the at least one polysaccharide.
 9. The compositionof claim 8, wherein the mixture comprises a dextrin and a molasses. 10.The composition of claim 9, wherein the dextrin exhibits a dextroseequivalent of greater than or equal to
 5. 11. The composition of claim10, wherein the dextrin exhibits a dextrose equivalent of less than 100.12. The composition of claim 10, wherein the dextrin exhibits a dextroseequivalent of greater than or equal to
 10. 13. The composition of claim12, wherein the dextrin exhibits a dextrose equivalent of greater thanor equal to
 15. 14. The composition of claim 1, wherein the at least onenon-polymeric organic polycarboxylic acid is a saturated or unsaturatedand linear or branched alicyclic acid, a cyclic acid or an aromaticacid.
 15. The composition of claim 1, wherein the at least onemonosaccharide and/or the at least one polysaccharide represents from 10to 90% of the weight of the mixture composed of the at least onemonosaccharide and/or the at least one polysaccharide and the at leastone non-polymeric organic polycarboxylic acid.
 16. The composition ofclaim 15, wherein the at least one monosaccharide and/or the at leastone polysaccharide represents from 20 to 85% of the weight of themixture composed of the at least one monosaccharide and/or the at leastone polysaccharide and the at least one non-polymeric organicpolycarboxylic acid.
 17. The composition of claim 16, wherein the atleast one monosaccharide and/or the at least one polysacchariderepresents from 30 to 80% of the weight of the mixture composed of theat least one monosaccharide and/or the at least one polysaccharide andthe at least one non-polymeric organic polycarboxylic acid.
 18. Thecomposition of claim 1, comprising a catalyst chosen from Lewis acidsand bases, phosphorus-comprising compounds and compounds comprisingfluorine and boron.
 19. The composition of claim 18, wherein thecatalyst represents up to 20% of the weight of the mixture of the atleast one monosaccharide and/or the at least one polysaccharide and theat least one non-polymeric organic polycarboxylic acid.
 20. Thecomposition of claim 19, wherein the catalyst represents up to 10% ofthe weight of the mixture of the at least one monosaccharide and/or theat least one polysaccharide and the at least one non-polymeric organicpolycarboxylic acid.
 21. The composition of claim 19, wherein thecatalyst represents at least 1% of the weight of the mixture of the atleast one monosaccharide and/or the at least one polysaccharide and theat least one non-polymeric organic polycarboxylic acid.
 22. Thecomposition of claim 1, comprising the additives below in the followingproportions, calculated on the basis of 100 parts by weight of the atleast one monosaccharide and/or the at least one polysaccharide and theat least one non-polymeric organic polycarboxylic acid: from 0 to 2parts of silane, from 0 to 20 parts of oil, from 0 to 30 parts of ureaand/or of glycerol, from 0 to 5 parts of a silicone, from 0 to 30 partsof an extender chosen from lignin derivatives, and animal or plantproteins.
 23. The composition of claim 22, wherein the proportion of oilis from 4 to 15 parts and the proportion of urea and/or glycerol is from0 to 20 parts.
 24. The composition of claim 22, wherein the silane isaminosilane.
 25. The composition of claim 22, wherein the ligninderivatives include an ammonium lignosulphonate or a sodiumlignosulphonate.
 26. An acoustic and/or thermal insulating product basedon mineral wool, sized using the sizing composition of claim
 1. 27. Aprocess for the manufacture of an acoustic and/or thermal insulatingproduct based on mineral wool as claimed in claim 26, according to whichthe mineral wool is manufactured, the process comprising projecting asizing composition onto said wool and treating said wool at atemperature which makes possible the crosslinking of the size and theformation of an infusible binder, wherein the sizing compositioncomprises: at least one monosaccharide and/or at least onepolysaccharide having a weight-average molar mass of less than 10000,and at least one non-polymeric organic polycarboxylic acid having amolar mass of less than 1000, wherein the at least one non-polymericorganic polycarboxylic acid represents at least 10% of a weight of themixture composed of the at least one monosaccharide and/or the at leastone polysaccharide and the at least one non-polymeric organicpolycarboxylic acid.
 28. A veil of mineral fibres, sized using thesizing composition of claim
 1. 29. A process for the manufacture of anacoustic and/or thermal insulating product based on a veil of mineralfibers as claimed in claim 28, according to which the mineral fibers aremanufactured, the process comprising projecting a sizing compositiononto said fibres and treating said fibres at a temperature which makespossible the crosslinking of the size and the formation of an infusiblebinder, wherein the sizing composition comprises: at least onemonosaccharide and/or at least one polysaccharide having aweight-average molar mass of less than 10000, and at least onenon-polymeric organic polycarboxylic acid having a molar mass of lessthan 1000, wherein the at least one non-polymeric organic polycarboxylicacid represents at least 10% of a weight of the mixture composed of theat least one monosaccharide and/or the at least one polysaccharide andthe at least one non-polymeric organic polycarboxylic acid.
 30. Thecomposition of claim 1, wherein the at least one polysaccharide exhibitsa weight-average molar mass of greater than
 180. 31. The composition ofclaim 1, wherein the at least one non-polymeric organic polycarboxylicacid comprises at most 4 carboxyl functional groups.
 32. The compositionof claim 31, wherein the at least one non-polymeric organicpolycarboxylic acid comprises at most 3 carboxyl functional groups. 33.The composition of claim 1, wherein the mineral wool is based on rock orglass.
 34. The composition of claim 1, wherein the at least onenon-polymeric organic polycarboxylic acid has a molar mass of less than750.
 35. The composition of claim 1, wherein the at least onenon-polymeric organic polycarboxylic acid is selected from the groupconsisting of oxalic acid, malonic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid,fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoricacid, phthalic acid, tetrahydrophthalic acid, chlorendic acid,isophthalic acid, terephthalic acid, mesaconic acid, citraconic acid,citric acid, tricarballylic acid, 1,2,4-butanetricarboxylic acid,aconitic acid, hemimellitic acid, trimellitic acid, trimesic acid,1,2,3,4-butanetetracarboxylic acid and pyromellitic acid.
 36. Thecomposition of claim 1, wherein the at least one non-polymeric organicpolycarboxylic acid represents at least 20% of the weight of the mixturecomposed of the at least one monosaccharide and/or the at least onepolysaccharide and the at least one non-polymeric organic polycarboxylicacid.
 37. A sizing composition for insulating products based on mineralwool, the composition comprising: a molasses, and at least onenon-polymeric organic polycarboxylic acid having a molar mass of lessthan 1000, wherein the molasses comprises from 40 to 60% by weight ofglucides, and wherein the at least one non-polymeric organicpolycarboxylic acid represents at least 10% of a weight of the mixturecomposed of the molasses and the at least one non-polymeric organicpolycarboxylic acid.
 38. The composition of claim 37, wherein themolasses comprises from 45 to 50% by weight of glucides.
 39. Thecomposition of claim 37, wherein the at least one non-polymeric organicpolycarboxylic acid represents at least 20% of the weight of the mixturecomposed of the at least one monosaccharide and/or the at least onepolysaccharide and the at least one non-polymeric organic polycarboxylicacid.
 40. A sizing composition for insulating products based on mineralwool, the composition comprising: at least one monosaccharide and/or atleast one polysaccharide having a weight-average molar mass of less than10000, and at least one non-polymeric organic polycarboxylic acid havinga molar mass of less than or equal to 750, wherein the at least onenon-polymeric organic polycarboxylic acid represents at least 10% of aweight of the mixture composed of the at least one monosaccharide and/orthe at least one polysaccharide and the at least one non-polymericorganic polycarboxylic acid.
 41. The composition of claim 40, whereinthe at least one non-polymeric polymeric organic polycarboxylic acidexhibits a molar mass of less than or equal to
 500. 42. The compositionof claim 40, wherein the at least one non-polymeric organicpolycarboxylic acid represents at least 20% of the weight of the mixturecomposed of the at least one monosaccharide and/or the at least onepolysaccharide and the at least one non-polymeric organic polycarboxylicacid.